Quinoline-azo compounds



Patented May 19, 1942 V i QUINOLINE-AZO COMPOUNDS William S. Jnes andWilliam Braker, Brooklyn, N. Y., assignors to E. R. Squibb & Sons, NewYork, N. Y., a corporation of New York a No Drawing. ApplicationDecember 23, 1939,

Serial No. 310,831 i Claims.

This invention relates to, and has for its object the provision of I,azo bases of the general formula wherein X represents hydroxy or(preferably) amino, and Y represents hydrogen, alkyl, aryl, hydroxy,alkoxy, or (preferably) amino; and II, acidaddition salts of these azobases.

These azo compounds are promising chemotherapeutic agents for thetreatment of pyelitis, urethritis, prostatitis, cystitis, and otheracute and chronic infections of the genito-urinary tract.Theacid-addition salts of the azo bases are water-soluble, and may beadministered orally. g

These azo bases may be prepared by diazotizing a5-amino-8-alkoXy-quinoline, especially a, 5- amino-8 [(lower alkyl) oxy]quinoline-inter alia, 5-amino-8-ethoxy-quinoline and 5-amino-8-butoxy-quinoline-and coupling the diazonium salt obtained with acompound of the general formula wherein X and Y have the meaning givenhereinbefore-inter alia, m-phenylene diamine, mphenetidine, aniline,phenol, resorcinol, m-cresol, m-phenyl-phenol, and m-toluidine.

The azo bases may be converted into acidaddition salts by reacting thebase with the appro priate acid in a solvent, e. g., alcohol or acetone,and recovering the salt formed, e. g., by evaporating the solvent. Theacids utilizable for preparation of such salts comprise inter alia,hydrochloric, sulfuric, boric, tartaric, lactic, citric, and malicacids.

The following examples are illustrative of the invention:

EXAMPLE 1 -5- (2',4 -diaminc-phenylaeo) 8-ethozwquinoline 1.4 g. of5-amino-8-ethoXy-quinoline is dissolved in 20 cc. of water containing 7cc. of concentrated hydrochloric acid, and diazotization is effected at0 C. with a solution of 0.38 g. of sodium nitrite in 10 cc. of water;then 0.775 g. of m-phenylene-diamine hydrochloride dissolved in cc. ofwater is added to the solution of the diazonium salt at 0 C., themixture is stirred vigorously for ten minutes, and the coupling reactionis allowed to proceed at 20 C. for two hours. The solution is madeammoniacal, and the precipitate is 001- lected, washed with water,anddried in a vacuum to yield 0.8 g. of a red base having the formulaC1'1I-I17N5O.

The hydrochloride (CmHmNsOCl) is obtained by adding 2.33 cc. of normalhydrochloric acid to a solution of 0.8 g. of the base in acetone, andevaporating the solution to dryness.

EXAMPLE 2 5- (2',4'-diamino-phenylazo) -8- butomy-quzlnoline 12.0 g. ofB-butQXy-quinoline is added in small portions and with constant stirringfor fifteen minutes to 45 cc. of nitric acid (density 1.5) at 0 C.; themixture is then vigorously agitated at 0 C. for'ten minutes, heated onasteam bath for twenty minutes, and pouredinto 170 cc. of water.Precipitation is effected by alkaliniz'ing the diluted solution, and theprecipitate is collected, washed with water, and dried in a vacuum toyield 10.2 g. of 5-nitro-8-butoxy-quinoline, having a melting point of111-112 C.

5.0 g. of this intermediate is dissolved in 20 cc. of concentratedhydrochloric acid contained in 25 cc. of water and the solution isheated to C. and added toa solution of 12.5 g. of stannous chloride in35 cc. of water; the mixture is then heated on a steam bath for 45minutes, cooled, the tin precipitated with hydrogen sulfide, the tinsulfide filtered off, and the filtrate is concentrated. Precipitation iseffected by cooling the concentratedfiltrate, and the precipitate iscollected, washed with cold 1:1 hydro chloric acid, and dried in avacuum to yield 5- amino-S-butoxy-quinoline dihydrochloride, hav- 7 andthe coupling reaction is allowed to proceed I at -5 C. for two hours andat 5 C. for twelve hours. Precipitation is effected with ammonia water,and the precipitate is collected, washed with water, and dried in avacuum to yield a red azo base having the empirical formula Thehydrochloride (C19H22N50C1) is obtained by adding the theoreticalquantity of hydrochloric acid to an alcoholic solution of the base, andevaporating the solution to dryness.

The invention may be variously otherwise embodied within the scope ofthe appended claims.

We claim:

1. A compound of the group consisting of: azo bases of the generalformula wherein Y represents a member of the group con sisting ofhydrogen, alkyl, phenyl, hydroxy, al-

2. An acid-addition salt of an azo base of the general formula wherein Yrepresents a member of the group consisting of hydrogen, alkyl, phenyl,hydroxy, alkoxy, and amino.

3. An acid-addition salt of an azo base of the general formula5-(2',4'-diamino-phenylazo) -8- (lower alkyl) -oxyl -quinoline.

4. An acid-addition salt of 5-(2',4-diaminophenylazo)-8-ethoxy-quinoline.

5. An acid-addition salt of 5-(2',4-diaminophenylazo)8-butoxy-quino1ine.

WILLIAM S. JONES. WILLIAM BRAKER.

